Partially fluorinated compounds and polymers

ABSTRACT

Partially fluorinated compounds of specified formulas that are useful as chemical intermediates and monomers are disclosed. Partially fluorinated polymers prepared from one of these compounds are also disclosed. Fluoro-2,2-dimethyldioxolanes and copolymers thereof are further disclosed.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a division of application Ser. No. 07/450,351 filedDec. 11, 1989, abandoned which is a continuation-in-part of U.S. Ser.No. 223,867, filed Jul. 25, 1988, now abandoned.

FIELD OF THE INVENTION

The present invention concerns partially fluorinated compounds which areuseful as chemical intermediates or monomers. The invention furtherconcerns partially fluorinated condensation polymers and dioxolanes.

BACKGROUND OF THE INVENTION

Fluorinated intermediates are employed in the synthesis of a variety ofchemical compounds, such as partially fluorinated polymers. Novelfluorinated intermediates and polymers derived therefrom are ofsignificant interest to the chemical industry.

Partially fluorinated condensation polymers are known in the literature,see. e.g., I. L. Knunyants, C. Li, and V. V. Shokina, Russ. Chem. Rev.,32:461 (1963), and the references described therein. These polymersgenerally have been made to obtain materials with improvedthermo-oxidative stability and solvent resistance, as compared tononfluorinated polymers.

Many partially fluorinated condensation polymers have been made withperfluoro diacids, HOOC--(CF₂)_(n) --COOH, as one component of thepolymer, see, e.g., B. S. Marks & G. C. Schweiker, J. Polymer Sci.43:229 (1960) wherein the synthesis of partially fluorinated polyamidescontaining perfluoro diacid units is disclosed. The polymers made fromsuch perfluoro diacids, however, suffer from problems associated withthe extreme hydrolytic instability of the perfluoroacyl functionalgroups. The strongly electron-withdrawing perfluoroalkyl group situatednext to the carbonyl of the perfluoroacyl group activates the carbonylto hydrolysis. It has been found that many of the resulting polymershydrolyze in moist air.

P. Johncock, S. P. Barnett, & P. A. Rickard, J. Polymer Sci./PolymerChem. 24:2033 (1986) disclose the synthesis of a diacid wherein thefluoroalkyl chain is separated from the acyl group by a methylenespacer, HOOC--CH₂ --(CF₂)₃ --CH₂ --COOH. Although polyesters made withthis diacid are more hydrolytically stable than those made fromperfluoro diacids, these compositions still hydrolyze under mildconditions. This acid also suffers from the ready loss of two moles ofhydrogen fluoride from the molecule.

P. L. Coe., N. E. Milner & J. A. Smith, J. Chem. Soc./Perkin I 654(1975) disclose use of perfluoroalkylcopper compounds to form certainpolyfluoroalkyl-substituted acids and alcohols. These compounds are saidto be of practical interest as surfactants. In one reaction,(1E,6E)-3,3,4,4,5,5-hexafluoro-1,7-di-iodohepta-1,6-diene was reactedwith copper(I) cyanide. Hydrolysis of the resulting unsaturateddinitrile yielded a diacid that was hydrogenated to give HOOC--CH₂ CH₂--(CF₂)₃ --CH₂ CH₂ --COOH.

U.S. Pat. No. 3,496,215 discloses hydrocyanation of unsaturatedcompounds using as a catalyst a compound of the structure Ni(PXYZ)₄wherein X is OR; Y and Z are R or OR; and R is an alkyl or aryl radicalof up to 18 carbon atoms. U.S. Pat. No. 3,496,217 discloseshydrocyanation of nonconjugated ethylenically unsaturated organiccompounds using certain nickel complexes as a catalyst and certain zinccontaining compounds as promoters. U.S. Pat. No. 3,496,218 discloseshydrocyanation of nonconjugated ethylenically unsaturated organiccompounds using certain nickel complexes as catalysts and certainorganoboron compounds as promoters.

C. A. Tolman et al., Adv. in Catalysis, 33:1 (1985) disclose homogeneousnickel-catalyzed olefin hydrocyanation, as well as unpromotedhydrocyanations of monoolefins and hydrocyanations promoted with Lewisacids.

The synthesis of compositions of the present invention starts withbis-2,2-trifluoromethyl-4,5-difluorodioxole, ##STR1## This dioxole wasclaimed by Resnick in U.S. Pat. No. 3,865,845.

SUMMARY OF THE INVENTION

The present invention provides compounds of the formula

    H.sub.2 C═CH--R.sub.f --CH.sub.2 CH.sub.2 --Y          (1)

wherein Y is selected from the group consisting of --CN, --CH₂ NH₂,--COOH, --CH₂ OH, --CH₂ N═C═O, --CONH₂, --CHO, --COCl, and --COOR,wherein R is C_(n) H_(2n+1) and n is an integer from 1 to 10, inclusive;and R_(f) is a fluorinated divalent organic radical selected from thegroup consisting of linear, branched, carbocyclic, and mixtures thereofhaving from 1 to about 40 carbon atoms.

The invention additionally provides compounds of the formula

    Y'-CH.sub.2 CH.sub.2 --R.sub.f --CH.sub.2 CH.sub.2 --Y'    (2)

wherein Y' is independently selected from the group consisting of --CN,--CH₂ NH₂, --CH₂ OH, --CH₂ N═C═O, --CONH₂, --CHO, --COCl, and --COOR,wherein R is C_(n) H_(2n+1) and n is an integer from 1 to 10, inclusive;and R_(f) is as defined above.

Compound (2) can be employed in a condensation type of polymerizationreaction to prepare polymers (A) and (B) of this invention. Polymer (A)can be either polymers comprising 100 mole percent of at least oneindependently selected repeating unit of the formula ##STR2## wherein Xis independently selected from the group consisting of NHCH₂ --, OCH₂--, --C(═O), and --CH₂ NH(C═O), X' is independently selected from thegroup consisting of NH--, O--, and --C(═O), provided that when X isNHCH₂ -- or OCH₂ --, X' must be --C(═O), and also provided that when Xis --C(═O) or --CH₂ NH(C═O), X' must be NH-- or O--; Z is any divalentorganic radical; and R_(f) is as defined above; or copolymers comprisingfrom 1 to 99 mole percent of at least one independently selectedrepeating unit of formula (3) and from 99 to 1 mole percent of at leastone independently selected repeating unit of the formula ##STR3##wherein X' and Z are as defined above, and Z is a independentlyselected, and X" is independently selected from the same group as X,provided that when X' is--C(═O), X" must be NH-- or O--, and alsoprovided that when X' is NH-- or O--, X" must be --C(═O). In thenomenclature for polymer (A), the dashes found in the X, X', and X"divalent groups indicate the side of the group that is attached eitherto --CH₂ CH₂ --R_(f) --CH₂ CH₂ -- in repeating unit (3) or to Z inrepeating units (3) and (4).

Polymer (B) can be either polymers comprising 100 mole percent of atleast one independently selected repeating unit of the formula ##STR4##wherein U is any tetravalent organic radical and R_(f) is as definedabove; or copolymers comprising from 1 to 99 mole percent of at leastone independently selected repeating unit of formula (5) and from 99 to1 mole percent of at least one independently selected repeating unit ofthe formula ##STR5## wherein U and Z are as defined above.

The invention also includes dioxolanes of the formula ##STR6## whereinD, E, G and J are:

    ______________________________________                                        D       E              G       J                                              ______________________________________                                        Cl      I              Cl      Cl                                             Br      H              Br      Cl                                             Br      Cl             Br      Cl                                             F       F              Cl      Cl                                             F       I              F       I                                              F       I              F       Br                                             F       I              F       Cl                                             F       I              F       F                                              F       Br             F       F                                              F       CH.sub.2 CH.sub.2 I                                                                          F       CH.sub.2 CH.sub.2 I                            F       CH.sub.2 CH.sub.2 I                                                                          F       F                                              F       CH.sub.2 CH.sub.2 I                                                                          F       Cl                                             F       CH.sub.2 CH.sub.2 I                                                                          F       Br                                             F       CH═CH.sub.2                                                                              F       CH═CH.sub.2                                F       CH═CH.sub.2                                                                              F       F                                              F       CH═CH.sub.2                                                                              F       Cl                                             F       CH═CH.sub.2                                                                              F       Br                                             F       COOH           F       F                                              F       COOH           F       Cl                                             F       COOH           F       Br                                             F       COCl           F       F                                              F       COF            F       F                                              F       CH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          F       CH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2            H       CH═CH.sub.2                                                                              H       CH═CH.sub.2                                H       CH.sub.2 CH.sub.2 CN                                                                         H       CH.sub.2 CH.sub.2 CN                           H       CH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          H       CH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2            ______________________________________                                    

Also included in the invention as new compositions of matter are##STR7##

The invention further includes copolymers of tetrafluoroethylene withthe above described dioxolane wherein D, E, G, and J are:

    ______________________________________                                        D         E            G        J                                             ______________________________________                                        F         CH═CH.sub.2                                                                            F        CH═CH.sub.2                               H         CH═CH.sub.2                                                                            H        CH═CH.sub.2                               F         CH═CH.sub.2                                                                            F        F                                             F         CH═CH.sub.2                                                                            F        Cl                                            F         CH═CH.sub.2                                                                            F        Br                                            ______________________________________                                    

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 plots the conversion of CH₂ ═CH--CF₂ CF₂ --CH═CH₂ against theselectivity to mononitrile and dinitrile. This shows that thehydrocyanation of a diene is sequential. In the figure, the crosses areexperimental points for mononitrile whereas the squares are experimentalpoints for dinitrile. The lines are theoretical fits resulting from theuse of a sequential kinetic model ##STR8## in the kinetic modelingcomputer program, GIT (available through the Quantum Chemistry ProgramExchange, Department of Chemistry, Indiana University, Bloomington,Ind.). The successful fit illustrates that k₁ is 3.5 times greater thank₂ and that essentially all dinitrile is derived from mononitrile.

DETAILED DESCRIPTION OF THE INVENTION

The halogen addition reactions of Examples 1-4 and 21, 23, 25, 27, and28 may be conducted at conditions of time and temperature sufficientlystrenuous to result in acceptable conversion of the starting materials,but not strenuous enough to result in low yield of the desired product.The mole ratio of the halogen to the dioxole may be 0.6 to 1.4,preferably 1:1.

The ethylene addition reactions of Examples 5, 7, 8, and 14, may bestarted at room temperature and heated gradually or rapidly to the finalreaction temperature of 200°-250°, preferably 220° as in the Examples.The time at temperature may be 0.5 to 24 hours, depending on thetemperature chosen. Longer time is needed at lower temperature.

The dehydrohalogenation reactions of Examples 6, 9, 10 and 15 use aconcentrated strong base, preferably KOH or NaOH, at 30°-60° for 10-24hours. Preferably a quaternary ammonium salt is added to a phasetransfer catalyst.

The oxidation of the vinyl compounds to carboxyl compounds, Examples 11,12 and 18, uses a permanganate salt at 25°-75°, continuing until theexothermic reaction is finished. Inorganic acid or a quaternary ammoniumsalt is an optional additive.

The polymerizations may be carried out in any of the methods known forpolymerization of tetrafluoroethylene, such as aqueous, nonaqueous, andtwo-phase. The temperature is selected to match the decomposition rateof the initiator chosen, which should be non-telogenic.

The copolymers, which contain at least 1 weight % of the vinyl compoundof this invention, are useful for electrical insulation, among otheruses. The compounds with five-membered rings are useful as monomers orintermediates to monomers. The product of Example 33 is useful as apolymer catalyst. The product of Example 34 is useful as startingmaterial for the preparation of solvents and stable fluids.

In the following examples, temperatures are in degrees Celsius.

The present invention provides partially fluorinated compounds which areuseful as chemical intermediates. The unsaturated nitrile compounds areuseful for the preparation of unsaturated acids, amines and esters. Theunsaturated nitriles and esters are intermediates for the production ofdinitriles and esternitriles of the present invention. The dinitrilecompounds are useful as intermediates for the production of diacids,diesters, diisocyanates, and diamines. The esternitrile compounds can bealso converted to esteramines. These difunctional species are useful forthe synthesis of partially fluorinated condensation polymers. Polymersprepared with compounds of the invention demonstrate improved hydrolyticstability and altered dielectric constants.

Compounds of the invention include compounds of the formula

    H.sub.2 C═CH--R.sub.f --CH.sub.2 CH.sub.2 --Y          (1)

wherein Y is selected from the group consisting of --CN, --CH₂ NH₂,--COOH, --CH₂ OH, --CH₂ N═C═O, --CONH₂, --CHO, --COCl, and --COOR,wherein R is C_(n) H_(2n+1) and n is an integer from 1 to 10, inclusive;and R_(f) is a fluorinated divalent organic radical selected from thegroup consisting of linear, branched, carbocyclic, and mixtures thereofhaving from 1 to about 40 carbon atoms.

Preferably, Y is --CN. In preferred embodiments, R_(f) is either thebranched and carbocyclic 4,5--(2,2-trifluoromethyl)-1,3-dioxolanediyl##STR9## (as shown in Example 14) or of the formula --(CF₂ CF₂)_(n) --wherein n is an integer from 1 to 6.

The invention additionally provides compounds of the formula

    Y'--CH.sub.2 CH.sub.2 --R.sub.f --CH.sub.2 CH.sub.2 --Y'   (2)

wherein Y' is independently selected from the group consisting of --CN,--CN₂ NH₂, --CH₂ OH, --CH₂ N═C═O, --CONH₂, --CHO, --COCl, and --COOR,wherein R is C_(n) H_(2n+1) ; and n is an integer from 1 to 10,inclusive; and R_(f) is as generally defined above.

Preferably, Y' is --CN. In preferred embodiments, R_(f) is either thebranched and carbocyclic 4,5-trifluoromethyl)-1,3-dioxolanediyl or ofthe formula --(CF₂ CF₂)_(n) -- wherein n is an integer from 1 to 6.

Compound (2) can be employed in a condensation type of polymerizationreaction to prepare polymers (A) and (B) of the invention. Polymer (A)results when Y' in compound (2) is --CH₂ NH₂, --CH₂ OH, --CH₂ N═C═O,--CONH₂, --COCl, or --COOR, wherein R is C_(n) H_(2n+1) and n is aninteger from 1 to 10. Additionally, HOOC--CH₂ CH₂ --R_(f) --CH₂ CH₂--COOH can be used to make polymer (A). Polymer (A) can be eitherpolymers comprising 100 mole percent of at least one independentlyselected repeating unit of the formula ##STR10## wherein X isindependently selected from the group consisting of NHCH₂ --, OCH₂ --,--C(═O), and --CH₂ NH(C═O); X' is independently selected from the groupconsisting of NH--, O--, and --C(═O), provided that when X is NHCH₂ --or OCH₂ --, X' must be --C(═O), and also provided that when X is --C(═O)or --CH₂ NH(C═O), X' must be NH-- or O--; Z is any divalent organicradical; and R_(f) is as generally defined above; or copolymerscomprising from 1 to 99 mole percent of at least one independentlyselected repeating unit of formula (3) and from 99 to 1 mole percent ofat least one independently selected repeating unit of the formula##STR11## wherein X' and Z are as defined above, and Z is independentlyselected, and X" is independently selected from the same group as X',provided that when X' is --C(═O), X" must be NH-- or O--, and alsoprovided that when X' is NH-- or O--, X" must be --C(═O). In thenomenclature for polymer (A), the dashes found in the X, X' and X"divalent groups indicate the side of the group that is attached eitherto --CH₂ CH₂ --R_(f) --CH₂ CH₂ -- in repeating unit (3) or to Z inrepeating units (3) and (4).

In repeating unit (3), the preferred R_(f) is either the branched andcarbocyclic 4,5-(2,2-trifluoromethyl)-1,3-dioxolanediyl or of theformula--(CF₂ CF₂)_(n) --wherein n is an integer from 1 to 6. Apreferred Z group in repeating units (3) and (4) is a divalent organicradical independently selected from the group consisting of linear,branched, carbocyclic, aromatic, and mixtures thereof having from 1 toabout 20 carbon atoms. Other preferred Z groups are --CH₂ CH₂ --R_(f)--CH₂ CH₂ --, provided that the X' or X" attached to --CH₂ CH₂ --R_(f)--CH₂ CH₂ -- is --C(═O), and --CH₂ CH₂ CH₂ --R_(f) --CH₂ CH₂ CH₂ --,provided that X' or X" attached to --CH₂ CH₂ CH₂ --R_(f) --CH₂ CH₂ CH₂-- is independently selected from the group consisting of --NH and --O,wherein R_(f) is as generally and specifically defined above. Anotherpreferred Z group is mesogenic divalent organic radicals. Mesogenicdivalent organic radicals can include, but are not limited to, divalentradicals of the formula

    --V--W--V--

wherein V is a divalent radical independently selected from the groupconsisting of 1,4-phenylene, 4,4'-biphenylene, naphthylidene,1,4-[2.2.2]-bicyclooctylidene, and 1,4-cyclohexylidene, and W is adivalent radical selected from the group consisting of --CH═N--,--N(O)═N--, --N═N--, --C(═O)--O--, --C═C--, --CH═CH--, --CH═C(CH₃)--,--C(═O)--NH--, --CH═CH--CH═N--, --CH═CH--C(═O)--O--, and --CH═N--N═CH--.The most preferred embodiment of Z is when Z is selected from the groupconsisting of --C₆ H₄ --, --C₁₀ H₆ --, and --(CH₂)_(n) --, wherein n isan integer from 2 to 20.

When Y' is --CH₂ NH₂ in compound (2), a condensation type ofpolymerization reaction can yield polymer (B). Polymer (B) can be eitherpolymers comprising 100 mole percent of at least one independentlyselected repeating unit of the formula ##STR12## wherein U is anytetravalent organic radical and R_(f) is as generally defined above; orcopolymers comprising 1 to 99 mole percent of at least one independentlyselected repeating unit of formula (5) and 99 to 1 mole percent of atleast one independently selected repeating unit of the formula ##STR13##wherein U and Z are as described above.

In repeating unit (5), the preferred R_(f) is either the branched andcarbocyclic 4,5--(2,2-trifluoromethyl)-1,3-dioxolanediyl or of theformula --(CF₂ CF₂)_(n) -- wherein n is an integer from 1 to 6. Apreferred U group in repeating units (5) and (6) is a divalent organicradical selected from the group consisting of linear, branched,carbocyclic, aromatic, and mixtures thereof having from about 6 to about20 carbon atoms and containing from 0 to about 5 sulfonyl linkages. Mostpreferred embodiments of U are 1,2,4,5-benzenetetrayl,2,2-bis(3,4-phenylene)-propane and2,2-bis(3,4-phenylene)-1,1,1,3,3,3-hexafluoropropane. In repeating unit(6), a preferred Z group is a divalent organic radical independentlyselected from the group consisting of linear, branched, carbocyclic,aromatic, and mixtures thereof having from 1 to about 20 carbon atoms.Other preferred embodiments of Z are m-phenylene and p-phenylene.

Compound (1) of the invention wherein Y is --CN can be made bycontacting CH₂ ═CH(R_(f))_(n) CH═CH₂ with HCN in the presence of anickel catalyst and a Lewis acid promoter such as zinc chloride by aprocess similar to that described in U.S. Pat. No. 3,496,217, thedisclosure of which is incorporated herein by reference. The dienestarting compound can be prepared by the method disclosed in Kim et al.,J. Fluor. Chem. 1:203 (1971) or by other conventional chemistry.

Compound (2) of the invention wherein one or both values for Y' is --CNcan be made by contacting compound (1) with HCN in a manner similar tothat described above. The addition of two equivalents of HCN to thediene to make compound (2), without isolation of the intermediatecompound (1), is sequential, i.e., the dinitrile is produced only fromthe mononitrile. The kinetic analysis shown in FIG. 1 wherein R_(f) is--CF₂ CF₂ -- illustrates this and shows that compound (2) is producedonly from compound (1). Similar analyses have been carried out for manyother R_(f) values and produced the same result.

Other Y values for compounds (1) and (2) result from converting the --CNgroup to other useful functional groups by conventional chemistry. Forexample, the --CN group can be converted to the --CH₂ NH₂ group byreaction with hydrogen in the presence of ammonia and Raney cobalt. The--CONH₂ group can be prepared by reaction of the --CN group with waterin the presence of sulfuric acid. The --COOH group can be prepared byheating the --CN group in 50% sulfuric acid in water. The --COCl groupcan be made by reacting the --COOH group with a reagent such as thionylchloride or phosphorus pentachloride. The --COOR group can be made byheating the --CN group in ROH solution in the presence of sulfuric acid.The --CHO group can be made by partially reducing the --COOR group witha reagent such as lithium tri-t-butoxyaluminum hydride. The --CH₂ OHgroup can be made by the reduction of the --COOR, or --COOH group, e.g.,by reacting with lithium aluminum hydride. The --CH₂ N═C═O group can beprepared by the reaction of the --CH₂ NH₂ group with phosgene.

Compound (1) of the invention has utility for the preparation of thedifunctional compound (2). Compound (2) of the invention is useful as anintermediate for the synthesis of polymer (A) and polymer (B) of theinvention by condensation type polymerization. Partially fluorinatedpolyamides can be made by heating a salt of the desired acid and amineand allowing the water formed in the reaction to distill off. Highermolecular weights can be obtained by vacuum finishing the molten polymerusing standard techniques. Polyesters of the invention can be made byheating a partially fluorinated free acid with the diacetate of a diolusing calcium acetate as a catalyst. Polyimides of the invention can bemade by adding a dianhydride to a solution of partially fluorinateddiamine in a solvent such as dimethylacetamide (DMAC). The resultingamidacid can be cast as a film and imidized by heating in a vacuum.

Methods for conducting condensation type polymerization are well knownin the art. For example, 4,4,5,5-tetrafluorosuberic acid can bepolymerized with hexamethylenediamine by heating a salt prepared fromthese materials. Also, 4,4,5,5,6,6,7,7-octofluorosebecic acid can bepolymerized with 1,4-butanediol diacetate by heating in the presence ofcalcium acetate as a catalyst. Most examples of polymer (A) are moldableor melt processible, and most examples of polymer (B) can be processedlike other polyimides.

It has been found that incorporation of compound (2) as a monomerimproves the thermal characteristics of the resulting polymers (A) and(B). For example, poly(hexamethylenesuberamide) has a melting point of232° C., whereas poly(hexamethylene-4,4,5,5-tetrafluorosuberamide) has amelting point of 268° C. This increase in melting point is evident alsoin polyesters. For example, poly(tetramethylenesuberate) melts at 60°C., whereas poly(tetramethylene-4,4,5,5-tetrafluorosuberate) melts at123° C.

The partially fluorinated compounds of the invention can increase theanisotropic range of polymers in which they are incorporated as amonomer. For example,poly(oxydecanedioyloxy-1,4-phenylene-2-methylvinylene-1,4-phenylene)melts at 210° C. to a nematic anisotropic phase. The resulting meltbecomes isotropic at 254° C., with an anistropic range of 44° C. Incontrast,poly(oxyoctafluorodecanediooyloxy-1,4-phenylene-2-methylvinylene-1,4-phenylene)melts at 153° C. to a more highly ordered, smectic anisotopic state. Theresulting melt becomes isotropic at 280° C., with an anisotropic rangeof 127° C.

The partially fluorinated compounds of this invention can alter thesolubility properties of polymers in which they are incorporated as amonomer. For example, wherepoly(oxydecanedioyloxy-1,4-phenylene-2-methylvinylene-1,4-phenylene) issoluble in chloroform,poly(oxyoctafluorodecanedioyloxy-1,4-phenylene-2-methylvinylene-1,4-phenylene)is insoluble in all common organic non-acid solvents. The compounds andpolymers of the present invention are described in the followingexamples.

EXAMPLES Part A

In this part of the Examples section, there is disclosed and taught thepreparation of various dioxolanes of the invention. Several of thesedioxolanes are subsequently employed in the preparation of the partiallyfluorinated compounds and polymers of the invention which are thesubject of the examples of Part B herein.

EXAMPLE 1 Preparation ofBis-2,2-trifluoromethyl-4,5-difluoro-4,5-diiodo-1,3-dioxolane (I)

A mixture of 54 g. iodine and 52 g.2,2-bis-trifluoromethyl-4,5-difluorodioxole, (II) was heated in a tubefor four hours at 100°. The product was filtered and distilled to give67.2 g. (I), boiling at 44°-45° at 10 torr. The ¹⁹ F NMR spectrum [transisomer -26.7 (2F), -79.0 (6F); cis isomer -39.5 (2F), -77.8 (3F), -79.0(3F)] and the infrared spectrum were consistent with structure (I).

EXAMPLE 2 Preparation ofBis-2,2-trifluoromethyl-4-bromo-5-iodo-4,5-difluoro-1,3-dioxolane (III)

(II), 98 g., was slowly added to a mixture of 83 g. iodine bromide and100 ml. 1,1,2-trichloro-1,2,2-trifluoroethane. The reaction mixture wastreated with aqueous sodium bisulfite and distilled to give 97.8 g.(III), boiling at 64° at 50 torr. The ¹⁹ F NMR spectrum [trans isomer-32.5 (1F), -33.9 (1F), -79.0 and -79.8 (6F); cis isomer -38.0 (1F),-53.1 (1F), -79.0 and 79.8 (6F)] and the infrared spectrum wereconsistent with structure (III).

EXAMPLE 3 Preparation ofBis-2,2-trifluoromethyl-4-chloro-5-iodo-4,5-difluoro-1,3-dioxolane (IV)

A mixture of 49 g. iodine monochloride and 48.8 g. (II) was heated in atube at 100° for four hours. The product was treated with aqueous sodiumbisulfite and distilled to give 49.2 g. (IV) boiling at 50° at 50 torr.The ¹⁹ F NMR spectrum [trans isomer -36.4 (1F), -40.0 (1F), -80.2 (6F);cis isomer -38.3 (1F), -61.7 (1F), -79.5 (3F), -80.2 (3F)] and theinfrared spectrum were consistent with structure (IV).

EXAMPLE 4 Preparation ofBis-2,2-trifluoromethyl-4,4,5-trifluoro-5-iodo-1,3-dioxolane (V)

Iodine pentafluoride, 6.1 g., was added to a mixture of 12.8 g. iodineand 50 ml. 1,1,2-trichloro-1,2,2-trifluoroethane. After stirring 30.5 g.(II) was added, stirred at room temperature for 16 hours and heated toreflux for 2.5 hours. After cooling the reaction mixture was treatedwith aqueous sodium bisulfite and distilled to give 2.1 g. (V) boilingat 40° at 100 torr. The ¹⁹ F NMR spectrum [-46.7 (1F), -60.4 and -87.3AB (2F) J_(AB) ═127 Hz., -80.9 (6F)] was consistent with structure (V).

EXAMPLE 5 Preparation of ##STR14##

A mixture of 66.0 g. (I) and 15 g. of ethylene was heated at 150° for 30minutes, 200° for 30 minutes and 220° for 10 hours. The product wasdistilled to give 47.0 g. (VI) boiling at 105° at 4 torr. The ¹⁹ F NMRspectrum [trans isomer -79.4 (6F), -106.8 (2F); cis isomer -79.4 (3F),-80.5 (3F), -109.0 (2F)], ¹ H NMR spectrum [3.6 (4H), 2.95 (4H)] andinfrared spectrum were consistent with structure (VI).

EXAMPLE 6 Preparation of ##STR15##

A mixture of 100 ml. 50% aqueous potassium hydroxide, 0.9 g.bis(2-hydroxypropyl)benzyldodecylammonium chloride, (VIII), and 46.2 g.(VI) was heated at 50° for 16 hours. The reaction mixture was distilledand the lower layer redistilled to give 19.1 g. (VII) boiling at 130°.The infrared spectrum, ¹⁹ F NMR spectrum [-79.6 (6F), -108.2 (2F)] and1H NMR spectrum were consistent with structure (VII).

EXAMPLE 7 Preparation of ##STR16##

A mixture of 95.0 g. (III) and 10 g. ethylene was heated at 220° forfour hours. The product was distilled to give 87.1 g. (IX) boiling at86° at 20 torr. The infrared and NMR spectra [¹ H 3.7 (2H), 3.2 (2H); ¹⁹F trans isomer -53.0 (1F), -79.4 (3F), -80.0 (3F), -94.5 (1F); cisisomer -55.9 (1F), -79.4 (3F), -80.0 (3F), -105.6 (1F) were consistentwith structure (IX).

EXAMPLE 8 Preparation of ##STR17##

A mixture of 28.5 g. (IV), 51.9 g. 1,1,2-trichloro-1.2.2-trifluoroethaneand 10 g. ethylene was heated at 150° for 30 minutes, 200° for 30minutes and 220° for 10 hours. The product was distilled to give 29.8 g.(X) boiling at 80°-82° at 25 torr. The infrared and NMR spectra [¹ H 3.5(2H), 3.0 (2H); ¹⁹ F trans isomer -59.2 (1F), -80.0 (3F), -80.5 (3F),-99.2 (1F); cis isomer -63.9 (1F), -80.0 (3F), -80.5 (3F), -105.8 (1F)]were consistent with structure (X).

EXAMPLE 9 Preparation of ##STR18##

A mixture of 50 ml. 50% aqueous sodium hydroxide, 0.6 g. (VIII), and29.8 g. (X) was heated at 45°-50° for 16 hours. The reaction mixture wasdistilled to give 19.1 g. (XI) as a lower layer, b.p. 108°. The ¹ H[complex peaks 5.2 to 5.7] and ¹⁹ F NMR [trans isomer -57.9 (1F), -81.0(3F), -81.5 (3F), -102.2 (1F); cis isomer -66.5 (1F), -81.0 (3F), -81.5(3F), -106.7 (1F)] were consistent with structure (XI).

EXAMPLE 10 Preparation of ##STR19##

A mixture of 103 ml. 50% aqueous sodium hydroxide, 2.5 ml. of 60% (VIII)and 87.1 g. (IX) was heated at 50° for 16 hours. The mixture wasdistilled to give a liquid with two layers. The lower layer wasredistilled to give 40.7 g. (XII) boiling at 120°-122°. The infrared andNMR spectra [¹ H complex peaks 5.5 to 6.1; ¹⁹ F trans isomer -50.8 (1F),-79.7 (3F), -80.3 (3F), -97.1 (1F); cis isomer -57.3 (1F), -79.7 (3F),-80.3 (3F), -105.0 (1F)] were consistent with structure (XII).

EXAMPLE 11 Preparation of ##STR20##

A cooled mixture of 134 ml. water, 27 g. conc. sulfuric acid and 32 g.potassium permanganate was stirred and 16.6 g. (XI) added slowly. Themixture was heated slowly and an exothermic reaction took place at 50°.After cooling the potassium permanganate and manganese dioxide weredestroyed by reaction with aqueous sodium sulfite. The lower layer wasseparated and the upper layer extracted four times with 75 ml. ether.The combined ethereal extracts and lower layer were combined, dried withcalcium chloride and distilled to give 7.3 g. (XIII) boiling at 107° at40 torr. The infrared and NMR spectra [¹ H 11.15; ¹⁹ F trans isomer-58.0 (1F), -80.3 (3F), -81.1 (3F), -102.1 (1F); cis isomer -64.2 (1F),-80.3 (3F), -81.1 (3F), -107.8 (1F)] were consistent with structure(XIII).

EXAMPLE 12 Preparation of ##STR21##

A mixture of 177 ml. water, 74.3 g. potassium permanganate and 3.54 g.methyltrioctylammonium chloride was stirred and 40.7 g. (XII) added in45 minutes. The temperature rose to 52° and was maintained at 4°-45°with external cooling for 5 hours. After heating to 70° followed byimmediate cooling the mixture was allowed to stand at room temperaturefor 16 hours. After acidification with sulfuric acid the excesspotassium permanganate and manganese dioxide were destroyed with aqueoussodium bisulfite. The lower layer was separated and the upper layerextracted twice with 100 ml. ether The extracts were combined with thelower level, dried with anhydrous magnesium sulfate and distilled togive 22.4 g. (XIV) boiling at 99° at 20 torr. The ¹⁹ F NMR spectrum[trans isomer -53.8 (1F), -80.5 (6F), -98.0 (1F); cis isomer -58.5 (1F),-79.7 (3F), -80.5 (3F), -107.7 (1F)] was consistent with structure(XIV).

EXAMPLE 13 Preparation of ##STR22##

A mixture of 48.8 g.(II), 45 g. yellow mercuric oxide, 127 g. iodine, 12g. anhydrous hydrogen fluoride, 0.1 g. phenothiazine and 0.055 g.hydroquinone was heated in a stainless steel tube at 50° for two hours,the temperature raised to 125° over a two hour period and at 125° forthree hours. The reaction mixture was poured into ice water and thelower organic layer distilled to give 50.0 g., 64%, (XV) boiling at74°-76°. The ¹⁹ F NMR spectrum was consistent with structure (XV).

EXAMPLE 14 Preparation of ##STR23##

A mixture of 11.7 g. (XV) and 5.0 g. ethylene was heated in a stainlesssteel tube at 220° for 10 hours. The liquid product was distilled togive 7.0 g., 56%, (XVI) boiling at 95° at 100 torr. The NMR spectra [¹ H2 90 (2H), 3.43 (2H); ¹⁹ F -77.8 (1F), -80.9 (3F), -81.6 (3F), -88.3(1F), -110.0 (1F)] are consistent with structure (XVI).

EXAMPLE 15 Preparation of ##STR24##

A mixture of 16.7 g. (XVI), 20 ml. 10M potassium hydroxide and 0.86 g.(VIII) was stirred at room temperature and monitored by gaschromatography until no more (XVI) remained. The lower organic layer wasseparated, washed with water, dilute hydrochloric acid and distilled togive 9.5 g., 82%, (XVII) boiling at 70°-72°. The NMR spectra [¹ H5.40-5.90 complex; ¹⁹ F -75.7 (1F), -82.0 (3F), -82.6 (3F), -90.3 (1F),-112.8 (1F)] are consistent with structure (XVII).

EXAMPLE 16 Copolymerization of (XVII) and Tetrafluoroethylene

A mixture of 5.0 g. (XVII), 30 g. of1,1,2-trichloro-1,2,2-trifluorethane, 0.05 g. "Percadox" 16N, 1.0 g.tetrafluoroethylene and 750 psi nitrogen was heated at 60° for 5 hours.The solvent was evaporated to yield 0.5 g. polymer containing 84.1 molepercent tetrafluoroethylene and 15.9 mole percent (XVII) as determinedby ¹⁹ F NMR spectroscopy.

EXAMPLE 17 Preparation of ##STR25##

A mixture of 97.6 g. (II), 90 g. yellow mercuric oxide, 160 g. bromine,36 g. anhydrous hydrogen fluoride, 0.2 g. phenothiazine and 0.11 g.hydroquinone was heated at 50° for two hours, the temperature raised to120° over a two hour period and held at 120° for three hours. Afterfiltration and washing with a saturated solution of sodium thiosulfatethe organic layer was distilled to give 13.5 g., (10%), (XVIII) boilingat 60° and 66 g., (41%),bis-2,2-trifluoromethyl4,5-dibromo-4,5-difluoro-1,3-dioxolane. The ¹⁹ FNMR spectrum [-54.5 (1F), -67.1 (1F), -81.6 (6F), -85.6 (1F)] isconsistent with structure (XVIII).

EXAMPLE 18 Preparation of ##STR26##

(XVII), 29.0 g, was slowly added to a mixture of 50 g. concentratedsulfuric acid, 100 ml. water and 31.6 g. potassium permanganate. Afterstirring for 6 hours at room temperature the reaction mixture wasextracted with ether, the organic layer washed with water and distilledto give 8.0 g., 26%, (XIX), boiling at 71°-71° [?] at 12-15 Torr. The ¹⁹F NMR spectrum [-74.8 (1F), -80.6 (6F), -84.5 (1F), -113.7 (1F)] isconsistent with structure (XIX).

EXAMPLE 19 Preparation of ##STR27##

Thionyl chloride, 14.3 g., was slowly added to a mixture of 30 g. (XIX)and 3.16 g. pyridine and slowly heated to 85°-90°. After heating at thistemperature for 1.5 hours the volatile product was codistilled withthionyl chloride and was separated in a separatory funnel. (XX), 15.0g., boiled at 79°-80°. The ¹⁹ F NMR spectrum [-74.5 (1F), -81.3 (3F),-81.8 (3F), -84.0 (1F), -109.1 (1F)] is consistent with structure (XX).

EXAMPLE 20 Preparation of ##STR28##

A mixture of 6.53 g. (XX), 4.06 g. potassium fluoride and 10 ml.tetramethylene sulfone was slowly heated to 140°. (XXI), 4.5 g., 72.6%,was obtained as a clear colorless oil boiling at approximately 50°. The¹⁹ F NMR spectrum [+23.9 (1F), -74.4 (1F), -81.2 (6F), -84.1 (1F),-113.3 (1F)] is consistent with structure (XXI).

EXAMPLE 21 Preparation of ##STR29##

Bromine was slowly added to 17.7 g. of2,2-bistrifluoromethyl-4-chloro-5-fluoro-1,3-dioxole under irradiationwith a sun lamp. The excess bromine was destroyed with aqueous sodiumbisulfite and the lower organic layer washed with water and distilled togive 16.8 g. (XXII) boiling at 85° at 100 torr. The infrared and ¹⁹ FNMR spectra [-28.5 (0.63F) trans, -34.8 (0.37F) cis, -77.8 to -80.0(6F)] are consistent with a mixture of cis and trans isomers of (XXII).

EXAMPLE 22 Preparation of ##STR30##

A mixture of 300 ml. isopropanol and 121.5 g.2,2-bis-trifluoromethyl-4,5-dibromo-4,5-difluoro-1,3-dioxolane wasirradiated with a sun lamp for 25 hours. The portion of the reactionmixture boiling from 52°-80° was washed with water and distilled to give50.0 g. of the cis and trans isomers of (XXIII) boiling at 90°. Theinfrared and NMR spectra [¹ H 6.06 (trans), 6.36 (cis); ¹⁹ F transisomer -53.5 (1F), -80.7 (6F), -113.8 (1F), cis isomer -63.3 (1F), -80.7(6F), -122.5 (1F)] are consistent with cis and trans isomers ofstructure (XXIII).

EXAMPLE 23 Preparation of ##STR31##

A mixture of 27.7 g. 2,2-bis-trifluoromethyl-4,5-dichloro-1,3-dioxoleand 18 g. iodine monochloride was irradiated with a sun lamp. Thereaction mixture was washed with aqueous sodium bisulfite and theorganic layer distilled to give 6.5 g. (XXIV) boiling at 61°-64° at 10torr. which slowly turned purple on standing. The infrared and ¹⁹ F NMRspectra [-76.4 complex] are consistent with structure (XXIV).

EXAMPLE 24 Preparation of 2,2-Bis-trifluoromethyl-4-chloro-1,3-dioxole(XXV)

A mixture 22.9 g. zinc dust and 120 ml. 2,2-ethoxyethoxyethanol wasstirred and 8 ml. 2,2-bis-trifluoromethyl-4,4,5-trichloro-1,3-dioxolane,(XXVI), added. After stirring at room temperature the reaction mixturewas heated to 55° and the remainder of (XXVI) was added slowly for atotal of 58.8 g. The mixture was stirred for 20 hours and thendistilled. The distillate was washed twice with water to give 36.3 g.(XXV) boiling at 75° whose infrared and ¹⁹ F NMR spectra were consistentwith structure (XXV).

EXAMPLE 25 Preparation of ##STR32##

Bromine was slowly added to 36.3 g. (XXV) while irradiating with a sunlamp. The excess bromine was destroyed with aqueous sodium bisulfite andthe organic layer was washed with water and distilled to give 51.9 g.(XXVII) boiling at 63° at 20 torr. The infrared and NMR [¹ H 7.24(trans), 6.98 (cis); ¹⁹ F -77.7, -78.6] spectra are consistent with thecis and trans isomers of structure (XXVII).

EXAMPLE 26 Preparation of ##STR33##

A mixture of 51.9 g. (XXVII), 4.0 g. antimony pentachloride and 25 g.anhydrous hydrogen fluoride was heated at 70° for one hour and 100° forthree hours and added to a mixture of ice and water. The lower layer wasseparated and distilled to give 15.7 g. (XXVIII) boiling at 118°. Theinfrared, mass and NMR [¹ H 6.85; ¹⁹ F -47.2 (1F), -78.9 (3F), -80.6(3F)] spectra are consistent with structure (XXVIII).

EXAMPLE 27 Preparation of ##STR34##

A 15.6 g. mixture of 2,2-bis-trifluoromethyl-1,3-dioxole and2,2-bis-trifluoromethyl-4-chloro-1,3-dioxole was irradiated with a sunlamp. Bromine was added slowly and after 25 minutes the excess brominewas destroyed with aqueous sodium bisulfite. The organic layer waswashed with water, dried with calcium chloride and distilled to give(XXIX) boiling at 69° at 50 torr and (XXX) boiling at 78° at 50 torr.The NMR spectra were consistent with these structures. [(XXIX) ¹ H 7.02;¹⁹ F -77.7; (XXX) ¹ H 7.29; ¹⁹ F -77.6 (3F) -78.4 (3F)]

EXAMPLE 28 Preparation of ##STR35##

The procedure of Example 27 was followed and 65.0 g.2,2-bis-trifluoromethyl-4,5-dichloro-1,3-dioxole was brominated to give93.9 g. cis/trans (XXXI) boiling at 97° at 50 torr. The infrared and NMRspectra [¹⁹ F trans -76.5, cis -76.1 (3F), -76.8 (3F)] are consistentwith structure (XXXI).

EXAMPLE 29 Preparation of ##STR36##

A mixture of 43.8 g.2,2-bis-trifluoromethyl-4,4,5-trichloro-1,3-dioxolane, 5.0 g. antimonypentachloride and 25 g. anhydrous hydrogen fluoride was heated at 70°for one hour and 120° for five hours. The reaction mixture was pouredinto ice and water. The lower layer was separated and distilled to give13.4 g. (XXXII) boiling at 54° and 11.7 g. (XXXIII) boiling at 75°. TheNMR and infrared spectra were consistent with structures (XXXII) and(XXXIII). [NMR (XXXII) ¹ H 5.68; ¹⁹ F -77.6 (1F), -82.6 (3F), -83.2(3F), -90.2 (1F), -130.9 (1F); (XXXIII) ¹ H 6.18; ¹⁹ F -73.3 (1F), -78.0(1F), -81.1 (3F), -82.3 (3F)]

EXAMPLE 30 Preparation of ##STR37##

A glass ampoule containing 8.8 g. (XXXIII) and 8.4 g. chlorine wassealed and irradiated with a sun lamp for 16 hours. The tube was opened,washed with aqueous sodium bisulfite, water and distilled to give 4.7 g.(XXXIV) boiling at 86°. The infrared and NMR [¹⁹ F -71.1 (2F), -80.8(6F)] spectra were consistent with structure (XXXIV).

EXAMPLE 31 Copolymerization of Tetrafluoroethylene and (VII)

A mixture of 12.1 g. (VII), 0.2 g. bis(4-t-butylcyclohexyl)peroxydicarbonate, (XXXV), 45 g. tetrafluoroethylene and 100 ml.1,1,2-trichloro-1,2,2-trifluoroethane was heated at 60° for one hour.70° for one hour and 80° for one hour. The reaction mixture wasevaporated to give a solid residue which was washed with anacetone/water mixture and then acetone. It was dried to yield 7.3 g. ofa white solid whose infrared spectrum was consistent with a copolymer of(VII) and tetrafluoroethylene.

EXAMPLE 32 Copolymerization of Tetrafluoroethylene and (XI)

A mixture of 200 ml. of water, 1.0 g. ammonium perfluorononanoate, 0.2g. ammonium persulfate, 10 g. (XI) and 45 g. tetrafluoroethylene washeated at 80° for one hour and 90° for two hours. The reaction mixture,which contained a liquid and solid, was stirred vigorously with a fewdrops of triethylenetetramine to give additional copolymer and filtered.

EXAMPLE 33 Preparation of ##STR38##

A mixture of 1.22 g. (II), 10 ml. tetrahydrofuran, and 1.38 g.tris(dimethylamino)sulfonium difluorotrimethyl silicate, (XXXVII), wasstirred at -70° and allowed to warm to room temperature. The volatileswere removed to give 1.96 g. residue which was recrystallized to give1.45 g. (XXXVI) melting at 99°-104°. The ¹⁹ F NMR spectrum [-45.6 (1F),-69 (3F), -71.3 (3F), -73.1 (1F), -77.3 (1F)] is consistent withstructure (XXXVI).

EXAMPLE 34 Preparation of ##STR39##

A mixture of 3.18 g. (XXXVI) and 15 ml. ether was cooled to 0° and 1.06g. of boron trifluoride etherate was added. The reaction mixture washeated to 35° and (XXXVIII) removed from the cooled receiver. Theinfrared [--C═O at 1875 cm.⁻ 1] and ¹⁹ F NMR spectra [-69.67 (2F),-72.83 (6F)] were consistent with structure (XXXVIII). The solid residuefrom the reaction mixture was recrystallized from acetonitrile to give1.63 g. (87%) tris(dimethylamino)sulfonium tetrafluoroborate.

Part B

In the Examples, compounds (1) and (2) were prepared according to thefollowing general procedure. A 3-necked, round-bottom flask equippedwith an overhead mechanical stirrer, reflux condenser (used with a lowtemperature circulation bath), nitrogen bubbler, and rubber septum wascharged under nitrogen with the specified catalyst components, toluene,and the desired diene. The resulting mixture was heated in a 50° C. oilbath. Hydrogen cyanide was fed to the mixture by vapor transfer bypassing nitrogen gas through liquid hydrogen cyanide cooled to 0° C. inan ice bath. Under these conditions, the saturated vapor mixture wasapproximately 30-40% hydrogen cyanide. The hydrogen cyanide vapor wasadmitted to the reaction vessel via a syringe needle passed through therubber septum and placed slightly above the liquid level. The vaporabsorbed into the reaction mixture. The reflux condenser was cooled to-14° C. to prevent escape of nonabsorbed hydrogen cyanide. Progress ofreactions was monitored by removing samples with a syringe, dilutingwith acetone, and analyzing by capillary gas chromatography(cross-linked methyl silicone column, 25 m, 0.2 mm inner diameter).

EXAMPLE 35 Preparation of H₂ C═CH--(CF₂)₂ --CH₂ CH₂ --CN and NC--CH₂ CH₂--(CF₂)₂ --CH₂ CH₂ --CN

A reaction mixture comprised of Ni(p-TTP)₄ (0.30 g; 0.20 mmol), p-TTP(0.25 mL; 0.82 mmol) (wherein p-TTP is tri-p-tolylphosphite), toluene(8.0 mL), BPh₃ (0.05 g; 0.2 mmol), and CH₂ ═CH(CF₂)₂ CH═CH₂ (2.24 g;0.45 mmol) was treated at 50° C. with hydrogen cyanide (nitrogen flow=4mL/min) as described in the general procedure above. Two new peaks whichgrew with time were observed by capillary gas chromatography (CGC).White solid began to form in the reaction mixture after 1.5 hours. Thereaction was stopped, and the white solid was found to be associatedwith the longer retention time new peak. Subsequent analysis revealedthat the new Peaks were associated with H₂ C═CH--(CF₂)₂ --CH₂ CH₂ --CNand NC--CH₂ CH₂ --(CF₂)₂ --CH₂ CH₂ --CN (the white solid).

EXAMPLE 36 Preparation of H₂ C═CH--(CF₂)₂ --CH₂ CH₂ --CN and NC--CH₂ CH₂--(CF₂)₂ --CH₂ CH₂ --CN

A reaction mixture comprised of Ni(TTP)₄ (7.0 mL, 5.6 mmol) (wherein TTPis tri-m,p-tolylphosphite), p-TTP (5.0 mL; 16.3 mmol), toluene (125 mL),ZnCl₂ (0.50 g; 3.7 mmol) and a mixture of CH₂ ═CH(CF₂)₂ CH═CH₂ andacetonitrile (55 g; 80:20) was treated at 50° C. with hydrogen cyanide(nitrogen flow=17 mL/min for 7.5 hours and then 7 mL/min untilcomplete). The reaction mixture was cooled, resulting in precipitationof a white solid. The mixture was filtered to remove the crudedinitrile. The solvent was then removed from the filtrate in vacuocausing more dinitrile to precipitate. The dinitrile was filtered andwashed with diethylether. The precipitates were combined andrecrystallized from methanol, yielding 25.4 g (34%) of white crystals,m.p. 109°-110° C. Fluorine NMR -116.7, m. Proton NMR 2-2.7, c. IR 2950cm⁻¹, w, (C--H); 2260 cm.sup. -1, m, (C.tbd.N); 1180 cm⁻¹, s, (C.tbd.F).The ether was removed from the filtrate in vacuo and the resulting oildistilled. H₂ C═CHC--(CF₂)₂ --CH₂ CH₂ --CN was collected, b.p. 60° C. at5 mm Hg, 37 g (57%). Proton NMR 6.7-7.2, c, (olefin); 5.6-6.2, c,(olefin); 2.1-2.8, c, (alkyl). Fluorine NMR -115.4, c, 2F; -116.75, c,2F. IR (neat) 3005 cm⁻¹, w, (C--H olefin); 2970 cm⁻¹, w, (C--H alkyl);2226 cm⁻¹, m, (C.tbd.N); 1655, m, (C═C); 1110 cm⁻¹, vs, (C--F).Elemental Analysis for NC--CH₂ CH₂ --(CF₂)₂ --CH₂ CH₂ --CN:

Calculated: %C 46.16; %H 3.87; %F 36.51;

Found: %C 45.90; %H 4.05; %F 36.22.

EXAMPLE 37 Preparation of NC--CH₂ CH₂ --(CF₂)₄ --CH₂ CH₂ --CN

A reaction mixture comprised of Ni(TTP)₄ (15.0 mL, 12.2 mmol), p-TTP (10mL; 32.6 mmol), toluene (250 mL), acetonitrile (20 mL), ZnCl₂ (1.0 g;7.4 mmol), and CH₂ ═CH(CF₂)₄ CH═CH₂ (161.5 g; 636 mmol) was treated at50° C. with hydrogen cyanide (nitrogen flow=40 mL/min for 1 hour, 32mL/min for 25 hours, and 16 mL/min for 3 hours). The reaction mixturewas cooled to -30° C. for about 18 hours and crude NC--CH₂ CH₂ --(CF₂)₄--CH₂ CH₂ --CN was isolated by filtration. The solvent was removed fromthe resulting filtrate in vacuo resulting in more white solid. Thesolids were redissolved in acetone and precipitated by addition ofpentane. The solid was isolated by filtration and recrystallized frommethanol producing white crystals (168 g; 86% yield) m.p. 66° -68° C.Fluorine NMR -116.0, c, 2F; -124.0, dd, 2F.

Elemental Analysis for NC--CH₂ CH₂ --(CF₂)₄ --CH₂ CH₂ --CN:

Calculated %C 38.97; %H 2.62; %F 49.32;

Found: %C 38.73; %H 2.75; %F 49.05.

EXAMPLE 38 Preparation of NC--CH₂ CH₂ --(CF₂)₆ --CH₂ CH₂ --CN

A reaction mixture comprised of Ni(p-TTP)₄ (1.0 g; 0.68 mmol), p-TTP(0.75 mL; 2.4 mmol), toluene (15 mL), BPh₃ (0.10 g; 0.41 mmol), and CH₂═CH(CF₂)₆ CH═CH₂ (9.0 mL; 13.3 g; 37.5 mmol) was treated at 50° C. withhydrogen cyanide (nitrogen flow=4 mL/min for 4 hours, 3.5 mL/min for 4hours, and 2 mL/min for about 18 hours). The entire reaction mixture wasredissolved in acetone filtered to remove the nickel containingcompounds. Hexanes were added to precipitate the product. The productwas filtered and the solids recrystallized from methanol to give whitecrystals of

NC--CH₂ CH₂ --(CF₂)₆ --CH₂ CH₂ --CN (6.8 g) m.p. 80°-81° C. Proton NMR2-2.8, c. Fluorine NMR -115.8, m, 2F; -122.3, m, 2F; -124.0, m, 2F.

Elemental Analysis for NC--CH₂ CH₂ --(CF₂)₆ --CH₂ CH₂ --CN:

Calculated: %C 33.09; %H 1.59; %F 59.81;

Found: %C 32.91; %H 1.58; %F 59.46.

EXAMPLE 39 Preparation of NC--CH₂ CH₂ --(CF₂)₈ --CH₂ CH₂ --CN

A reaction mixture comprised of Ni(TTP)₄ (7.0 mL, 5.6 mmol), p-TTP (5.0mL; 16.3 mmol), toluene (130 mL), acetonitrile (10 mL), ZnCl₂ (0.50 g;3.7 mmol), and CH₂ ═CH(CF₂)₈ CH═CH₂ (50 g, 110 mmol) was treated at 50°C. with hydrogen cyanide (nitrogen flow=18 mL/min for 3 hours and 13mL/min for 5 hours). The mixture was diluted with hexanes and cooled to-30° C. to crystallize the NC--CH₂ CH₂ --(CF₂)₈ --CH₂ CH₂ --CN. Thecrude product was dissolved in acetone and filtered through Celite toremove the spent catalyst. The acetone was then removed, and the productwas recrystallized from methanol. The yield was 46 g (82%).

EXAMPLE 40 Preparation of NC--CH₂ CH₂ --(CF₂)₈ --CH₂ CH₂ --CN

A reaction mixture comprised of Ni(TTP)₄ (20 mL, 16.3 mmol), p-TTP (10mL; 32.6 mmol) toluene (300 mL), acetonitrile (10 mL), ZnCl₂ (1.0 g; 7.4mmol), and CH₂ ═CH(CF₂)₈ CH═CH₂ (200 g; 440 mmol) was treated at 50° C.with hydrogen cyanide (nitrogen flow=35 mL/min) for 26 hours. Themixture was diluted with hexanes and cooled to -30° C. to crystallizeNC--CH₂ CH₂ --(CF₂)₈ --CH₂ CH₂ --CN. The crude product was dissolved inacetone and filtered through Celite to remove the spent catalyst. Theacetone was then removed, and the product was then recrystallized frommethanol. The yield was 202 g (90%).

EXAMPLE 41 Preparation of HOOC--CH₂ CH₂ --(CF₂)₂ --CH₂ CH₂ --COOH

NC--CH₂ CH₂ --(CF₂)₂ --CH₂ CH₂ --CN (1.0 g) was added to a solution of50 mL water and 50 mL of concentrated sulfuric acid. The resultingmixture was heated to 130° C. for 18 hours. Upon cooling to 0° C., whitecrystals formed. The crystals were filtered, washed with cold water, andrecrystallized from water. Yield 0.8 g white crystals, m.p. 204°-206° C.Proton NMR (acetone) 2.6, c. Fluorine NMR -115.8, dt. IR (KBr) 3500-2500cm⁻¹, br, (O--H), 1715 cm⁻¹, s, (C═O); 1200 cm⁻¹, vs, (C--F).

EXAMPLE 42 Preparation of HOOC--CH₂ CH₂ --(CF₂)₄ --CH₂ CH₂ --COOH

NC--CH₂ CH₂ --(CF₂)₄ --CH₂ CH₂ --CN (100 g) was added to 500 mL ofwater. Concentrated sulfuric acid (700 mL) was slowly added, and theresulting reaction mixture was heated to 150° C. for about 18 hours.Upon cooling to 0° C., crystals formed. The crystals were filtered,washed with water, and recrystallized from water with a hot filtrationthrough Celite. Yield 55 g of white crystals. IR 3500-2400 cm⁻¹, br;1710 cm⁻¹, s; 1250-1150 cm⁻¹, s..

EXAMPLE 43 Preparation of H₃ COOC--CH₂ CH₂ --(CF₂)₂ --CH₂ CH₂ --COOCH₃

HOOC--CH₂ CH₂ --(CF₂)₂ --CH₂ CH₂ --COOH (25 g) was dissolved in 100 mLmethanol. Concentrated sulfuric acid (10 mL) was added, and theresulting solution was refluxed for 4 hours, and then stirred at ambienttemperature for 2 days. The solution was cooled to 0° C. and crystalsformed. The crystals were filtered, washed with cold methanol, andrecrystallized from methanol. The resulting filtrate was added to 500 mLof water and extracted with 4 100 mL portions of ether. The ether layerswere washed with 100 mL water, 2 100 mL portions of 10% Na₂ CO₃, 2 100mL portions of water, and 100 mL of brine. The resulting solution wasdried over MgSO₄ and then stripped to give white crystals that wererecrystallized from methanol. Yield 23 g white crystals, m.p. 64°-66° C.IR (KBr) 1740 cm⁻¹, s, (C═O).

EXAMPLE 44 Preparation of H₃ COOC--CH₂ CH₂ --(CF₂)₂ --CH₂ CH₂ --COOCH₃

NC--CH₂ CH₂ --(CF₂)₂ --CH₂ CH₂ --CN (50 g) was dissolved in 200 mL ofmethanol. Concentrated sulfuric acid (150 mL) was added slowly and theresulting solution was refluxed for 6 hours. The solution was thendumped into 1 L of ice. The resulting mixture was extracted with 3 200mL portions of ether. The ether layers were washed with 2 100 mLportions of water and 50 mL of brine. The solution was dried over MgSO₄and then stripped to give white crystals which were recrystallized frommethanol. Yield 57 g (87%), m.p. 64°-65° C. IR (KBr) 2980 cm⁻¹, m; 1740cm⁻¹, s; 1200 cm⁻¹, s.

EXAMPLE 45 Preparation of NC--CH₂ CH₂ --(CF₂)₆ --CH₂ CH₂ --CN

The method described in Example 40 was substantially repeated exceptthat CH₂ ═CH(CF₂)₆ CH═CH₂ (200 g; 565 mmol) was hydrocyanated andNC--CH₂ CH₂ --(CF₂)₆ --CH₂ CH₂ --CN was produced. Yield 215 g (93%).

EXAMPLE 46 Preparation of H₂ N--CH₂ CH₂ CH₂ --(CF₂)₂ --CH₂ CH₂ CH₂ --NH₂

NC--CH₂ CH₂ --(CF₂)₂ --CH₂ CH₂ --CN (4.8 g) was dissolved in 200 mL ofTHF. This solution was placed in a 400 mL bomb. The bomb was cooled andevacuated. Ammonia (50 g) was added to the bomb and then hydrogen wasadded until the pressure was 1500 psi at ambient temperature. The bombwas sealed and heated to 110° C. for 10 hours. The bomb was cooled, andthe gasses were bled off. The resulting solution was filtered throughCelite and then stripped to a pale yellow oil. The oil was dissolved in300 mL of ether, and HCl gas was bubbled through the resulting solution.A white precipitate formed that was filtered, washed with ether, anddried. The precipitate was recrystallized from a mixture of methanol andethanol to give 5 g of white crystals. Fluorine NMR (D₂ O) -114.5, t.Proton NMR 3.0, t, 2H; 2.0, c, 4H.

EXAMPLE 47 Preparation of H₂ N--CH₂ CH₂ CH₂ --(CF₂)₈ --CH₂ CH₂ CH₂ --NH₂

NC--CH₂ CH₂ --(CF₂)₈ --CH₂ CH₂ --CN (50 g) was placed into a 400 mLbomb, along with 200 mL of THF and approximately 5 g of Raney cobalt.The bomb was sealed and 50 g of ammonia were added. Hydrogen was addedto a pressure of 500 psi at ambient temperature. The bomb was heated to110° C. and the hydrogen pressure was adjusted to 1500 psi. Thetemperature and hydrogen pressure were held constant for 18 hours. Thebomb was cooled, and the gasses were bled off. The solution was filteredthrough Celite, and the solvent was removed to give 13 g of a white waxysolid. Proton NMR (CDCl₃ /F11) 2.7, t, 38; 1.5-2.5, c, 87; 1.0, s, 42.Fluorine NMR -114.6, 2F, -122.3, 4F; -124.0, 2F. IR (KBr) 3400 cm⁻¹, m;3300 cm⁻¹, m; 3200 cm⁻¹, m; 2960 cm⁻¹, m; 1200 cm⁻¹, vs.

EXAMPLE 48 ##STR40##

A reaction mixture comprised of Ni(p-TTP)₄ (0.25 g; 0.17 mmol), p-TTP(0.5 mL; 1.6 mmol), toluene (5 mL), acetonitrile (0.2 mL), ZnCl₂ (0.005g; 0.038 mmol), and ##STR41## (1.0 g, 3.35 mmol) as treated at 50° C.with hydrogen cyanide (nitrogen flow=3 mL/min) for 20 hours. Theresulting reaction mixture was cooled and filtered through Celite. Gaschromatography analysis showed two new products. High resolution GC/MSshowed that the first product was ##STR42## and the second product was##STR43##

IR (reaction mixture) 2280 cm⁻¹, m; 2255 cm⁻¹, m; 1300-1100 cm⁻¹, vs.

EXAMPLE 49 Preparation of Partially Fluorinated Polyamide Polymer (A)

A 500 mL round-bottom flask was equipped with an overhead stirrer, anitrogen inlet, and a Liebig's condensor topped with a still head. Theflash was charged with 35 g of crystals of the salt oftetrafluorosuberic acid and hexamethylenediamine prepared according tothe following procedure. Tetrafluorosuberic acid (25.00 g) was dissolvedin 250 mL of hot ethanol, and 11.79 g of hexamethylenediamine weredissolved in 100 mL of hot ethanol. The resulting solutions werecombined to produce a suspension containing white crystals. Thesuspension was stirred for 10 minutes, cooled to 0° C., filtered, washedwith ethanol, and dried in vacuo to give 35.97 g of white crystals. Thismaterial was immediately immediately charged to the flask as describedabove.

The flask was heated to 220° C., and the water formed was allowed toreflux. Over a period of about 1 hour, the temperature of the flask wasraised to 290° C. The water in the condensor was drained. The waterformed in the reaction was allowed to distill off. Over the next hourthe temperature of the flask was slowly raised to 300° C., giving aviscous amber melt. The melt was allowed to cool, giving 30 g of anamber polymer.

The inherent viscosity of the polymer in a formic acid solution was 1.07dl/g. The polymer formed strong melt pressed films which had an aqueouscontact angle of 74°. The polymer was also spun to form strong fibers.The melting point of the polymer was 268° C., as compared to 232° C. forthe melting point of the nonfluorinated polymer.

EXAMPLE 50 Preparation of Partially Fluorinated Polyester Polymer (A)

A small polymer tube with a side arm was charged with 5.00 g ofdimethyltetrafluorosuberate, 1.81 g of butanediol, 3 mg of calciumacetate, and 1.5 mg of antimony oxide. The resuting mixture was degassedand heated to 200° C. A needle with a slow flow of nitrogen was put atthe bottom of the melt and the temperature was raised to 275° C. over aperiod of 3 hours and held there for 16 hours. During this time, firstmethanol and then butanediol slowly distilled from the resulting melt.The pressure was then reduced to about 1 mm Hg for a period of 30minutes. The melt was cooled to form an opaque white solid polymer.Fibers and melt pressed films could be made from the polymer. Theinherent viscosity of the melt in a chloroform solution was 0.28 dl/g.

The polymer had a melting point of 123° C. as compared to 60° C. fornonfluorinated polymer.

EXAMPLE 51 Preparation of Partially Fluorinated Polyimide Polymer (B)

Dodecafluoro-1,12-dodecadiamine (8.975 g) was dissolved in about 100 mLof N-methylpyrrolidone (NMP) in a 500 mL 3-necked flask equipped with anoverhead stirrer and a nitrogen inlet. Pyromelliticdianhydride (4.567 g)was added in several batches, producing a viscous solution containingsome gel. About 100 mL of NMP were added to dissolve some of the gel.The resulting solution was filtered through a 0.2 micron filter and caston a glass plate. The solvent was evaporated at 75° C. for about 18hours. The polymer was imidized by heating in vacuo at 150° C. for about16 hours and then at 175° C. for 4 hours to give a tough clear film. Thepolymer had a melting point of 341° C. and did not decompose below 450°C.

EXAMPLE 52 Preparation of Partially Fluorinated Liquid CrystallinePolyester Polymer (A)

Alpha-methylstilbenediol diacetate (2.62 g),hexadecafluorododecane-1,12-dicarboxylate (5.0 g), and 0.01 g sodiumacetate were added to a polymer tube with a side arm. The resultingmixture was melted in a metal bath at 200° C., and a needle with a slowpurge of nitrogen was placed at the bottom of the resulting melt. Themelt was held at 200° C. for 18 hours while acetic acid distilled off.The temperature was then raised to 250° C. for 5 hours. The nitrogenpurge was stopped, and the pressure was reduced to about 1 mm Hg for 1hour. The resulting combination was cooled to give an off-white solidpolymer. The polymer melted at 230° C. to a smectic anisotropic state.The resulting melt remained anisotropic until a temperature of 310° C.was reached, at which point the melt was isotropic. Upon cooling, thesmectic state returned at about 270° C., and remained anisotropic untilthe polymer hardened at about 220° C.

This polymer had an enantiotropic anisotropic range of 80° C., asopposed to a monotropic anisotropic range of 7° C. for the correspondingnonfluorinated polymer. The anisotropic state for the fluorinatedpolymer was in a more highly ordered smectic state, as compared to thenematic anisotropic state of the nonfluorinated polymer.

EXAMPLE 53 Preparation of Partially Fluorinated Liquid CrystallinePolyester Copolymer (A)

4,4'-diacetoxybenzoyl phenol (2.00 g), tetrafluorosuberic acid (1.91 g),and 0.01 g calcium acetate were placed in a small polymer tube with aside arm. The resulting mixture was heated to 250° C. and nitrogen wasslowly purged through the resulting melt for about 18 hours. The meltwas cooled to give an off-white polymer. Fibers could be pulled from themelt. The polymer melted at 215° C. to an anisotropic phase. It remainedanisotropic upon heating to 400° C. This yielded an anisotropic range ofgreater than 185° C., as compared to the nonfluorinated polymer, whichhad an anisotropic range of 115° C.

Part C

In this part of the Examples section, there is disclosed and taught thepreparation of additional dioxolanes according to the invention.Specifically, this part includes amine functionalized dioxolanes andpolymers of them.

EXAMPLE 54 Preparation of2,2-Bis(Trifluoromethyl)-4,5-Di(3-Aminopropyl)-4,5-Difluoro-1,3-Dioxolane

In a 1400 ml Hastelloy-C Shaker tube was charged the2,2-bis(trifluoromethyl)-4,5-di(2-cyanoethyl)-4,5-difluoro-1,3-dioxolaneof Example 43 (56.3 g, 0.16 mole), tetrahydrofuran (320 ml) andRaney-Cobalt catalyst (14.4 g). The tube was sealed and cool-evacuated.Ammonia (64 g, 3.765 mole) was transferred into the tube and the tubewas pressurized with hydrogen gas to 500 psi. The tube was then heatedto 110° C. and the hydrogen pressure was adjusted to 1500 psi. Theheating was continued for 18 hrs at this temperature. After the tube wascooled, the product mixture was filtered to remove the catalyst, andsolvent was removed in vacuo. The residue was distilled to give thedesired product 46 g (80% yield) as a clear, colorless, viscous liquid,Bp. 80° C./0.06 mmHg. H-1 NMR (CDCl₃): 3.02 (m, 4H), 2.30 (m, 4H), 1.97(m, 4H), 1.50 (s, br, --NH₂); F-19 NMR (CDCl₃): -80.5 (m, 6F), [-108.8(m, br, trans), -110.6 (m, br cis) (2F total)].

EXAMPLE 55 Preparation of2,2-Bis(Trifluoromethyl)-4,5-Divinyl-1,3-Dioxolane

2,3-Divinylethylene oxide was prepared according to E. L. Stogryn etal., J. Org. Chem., 29, 1275 (1964). This compound (60 g, 0.625 mole)was mixed with d-limonene (2 g), tetra-n-butylammonium bromide (0.6 g),water (0.6 g) and hexafluoroacetone (108 g, 0.65 mole) in a 360 mlShaker tube. The tube was sealed and was heated at 80° C./1 h4, 100°C./1hr and 120° C./6 hrs. The product mixture unloaded from the tube wasdistilled to give the desired product 30 g as a clear, colorless liquid.Bp. 50° C./30 mmHg. The structure was supported by its NMR spectroscopicdata.

EXAMPLE 56 Preparation of2,2-Bis(Trifluoromethyl)-4,5-Di(2--Cyanoethyl)-1,3-Dioxolane

A reaction mixture comprised of Ni(TPP)₄ (3.4 g), TTP (2.1 g), toluene(25 ml), 25% EtAlCl₂ /toluene (1.8M, 2.0 ml) and the compound of Example55 (24 g, 0.092 mole) was treated at 60° C. with a 50% HCN/toluenesolution at 1.5 ml/hr for 4.5 hrs and then 0.5 ml/hr until a gaschromatography showed complete conversion to the dinitrile. The mixturewas cooled and a white solid was formed. The solid was collected byfiltration and was dissolved in acetonitrile, washed with hexanes, afterdrying over magnesium sulfate, the solvent was removed and the residuewas recrystallized from methanol. 10 g of the desired product wasobtained. Mp. 58° to 59.5° C. H-1 NMR (CDCl₃): 2.06 (s, br, 4H), 2.64(s, Br, 4H), 4.20, 4.70 (2s, br, 2H); F-19 NMR (CDCl₃): -81.0 (s, br)and -80.2, -80.4 (2s, br).

EXAMPLE 57 Preparation of2,2-Bis(Trifluoromethyl)-4,5-Di(3-Aminopropyl)-1,3-Dioxolane

The compound of Example 56 (9.72 g, 0.031 mole) was mixed withtetrahydrofuran (60 ml), Raney-Cobalt (2.8 g) and ammonia (12 g, 0.706mole) in a 360 ml Hastelloy-C Shaker tube. The tube was pressurized withhydrogen to 500 psi at room temperature. The tube was then heated at110° C. for 18 hrs while the hydrogen pressure was adjusted to 1500 psiunder the reaction process. The product mixture was filtered first, thenwas distilled to give the desired product 4.3 g as a clear, colorlessliquid. Bp 85° C./0.02 mmHg. H-1 NMR (CDCl₃): 3.98 (s, br, 2H), 2.76 (t,J=6 Hz, 4H), 1.80-1.50 (m, 8H), 1.30 (s, br, 4H); F-19 NMR (CDCl₃):-81.1 (s, 6F).

EXAMPLE 58 Preparation of a Polyimide fromPMDA(1,2,4,5-Benzenetetracarboxylic Anhydride) by Chemical ImidizationMethod

In a dried flask was charged the compound of Example 54 (1.8 g, 0.005mole) in 1-methyl-2-pyrrolidinone (NMP) (18 g) solvent. The mixture wasstirred until all the compound was dissolved. The solid PMDA (1.09 g,0.005 mole/ was added under nitrogen atmosphere. The mixture was stirredfor 16 hrs at ambient temperature to give a polyamic acid solution.

In a separate flask, a mixture of NMP (10 ml), pyridine (1.08 g, 0.0137mole) and acetic anhydride (1.28 g, 0.0125 mole) was heated to 100° C.To this solution the polyamic acid solution prepared from above wasdripping in slowly. After the addition was complete, the mixture wasfurther stirred for 2 hrs at 100° C. After cooling, the product mixturewas poured into water with vigorous stirring. The solid precipitateformed was filtered, washed thoroughly with water and methanol. Then wasdried in a vacuum oven (ca. 150 mmHg) at 220° C. for 4 hrs to give avery pale-brown solid polymer (1.71 g). This polymer has shown a Tm at295° C. as determined by DSC measurement.

EXAMPLE 59 Preparation of a polyimide from6-FDA[4,4'-Hexafluoroisopropylidene)diphthalic Anhydride] by ThermalImidization Method

The polyamic acid solution was prepared as described above from thecompound of Example 54 (1.8 g, 0.005 mole) and 6-FDA (2.22 g, 0.005mole) in NMP solvent. Half amount of the polyamic acid solution formedwas imidized under the following thermal conditions: 100° C./0.5 hr,150° C./0.5 hr, 200° C./1 hr, 250° C./1 hr and finally 280° C./1 hr.After cooling, 1.37 g solid polyimide was obtained. This polyimide hasshown a Tg at 120° C. as measured by DSC. The structure of the polyimidewas confirmed by its H-1 and F-19 NMR spectroscopic data.

EXAMPLE 60 Preparation of a Polyimide from ODA-(4,4'-Oxydianiline) (7:3mole ratio)/PMDA

This polyimide was prepared from the compound of Example 54 (9 g, 0.025mole), ODA (11.66 g, 0.0583 mole) and PMDA (18.25 g, 0.0833 mole) inN,N-dimethylacetamide (DMAC) solvent (222 g). The resulting film fromthis polyimide with 41 μm thickness gave a tensile strength 84 MPa,elastic modulus 1200 MPa and 17% elongation.

What is claimed is:
 1. Dioxolanes of the formula ##STR44## wherein D, E,G and J are:

    ______________________________________                                        D       E              G       J                                              ______________________________________                                        Cl      I              Cl      Cl                                             Br      H              Br      Cl                                             Br      Cl             Br      Cl                                             F       F              Cl      Cl                                             F       I              F       I                                              F       I              F       Br                                             F       I              F       Cl                                             F       I              F       F                                              F       Br             F       F                                              F       CH.sub.2 CH.sub.2 I                                                                          F       CH.sub.2 CH.sub.2 I                            F       CH.sub.2 CH.sub.2 I                                                                          F       F                                              F       CH.sub.2 CH.sub.2 I                                                                          F       Cl                                             F       CH.sub.2 CH.sub.2 I                                                                          F       Br                                             F       CH═CH.sub.2                                                                              F       CH═CH.sub.2                                F       CH═CH.sub.2                                                                              F       F                                              F       CH═CH.sub.2                                                                              F       Cl                                             F       CH═CH.sub.2                                                                              F       Br                                             F       COOH           F       F                                              F       COOH           F       Cl                                             F       COOH           F       Br                                             F       COCl           F       F                                              F       COF            F       F                                              H       CH═CH.sub.2                                                                              H       CH═CH.sub.2                                H       CH.sub.2 CH.sub.2 CN                                                                         H       CH.sub.2 CH.sub.2 CN                           H       CH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          H       CH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2.           ______________________________________                                    